Dry cleaning compositions



2,980,624 DRY CLEANING COMPOSITlONS John P; Miller 111, Bloomfield,-'NJ.',- assignor to General Aniline & Film Corporation, New York, NY a corporation of Delaware I No Drawing. Filed Jan. 4, 1957, Ser. No. 632,415

15 Claims. (Cl. 252-152) This invention relates to improvements in the dry cleaning of fibrous textiles and related materials and more particularly to new and improved compositions for use with dry cleaning solvents, and to processes of dry cleaning wherein said improved compositions are employed.

It is well known that many types of fabrics and materials cannot be cleaned by the ordinary means of soap or detergents and water, such as areemployed in laundering type operations since the presence of water deleteriously affects such materials. To provide effective cleaning for such materials, a dry cleaning process must be used. Dry cleaning processes employ organic solvents which are eifective in removing from the materials treated most of the undesirable dirt, grease, dust and the like. It is also a common expedient in dry cleaning processes to add a small amount of water which, sufficiently dispersed in the dry cleaning fluid, will be effective to remove water-soluble stains without adversely affecting the material treated.

It is therefore an object of this invention to provide new compositions, particularly suitable for use in dry cleaning operations.

It is a further object of this invention to provide new compositions suitable for use in chlorinated dry cleaning solvents. I

It is a still further object of this invention to provide new compositions which give outstanding and improved cleaning ability by virtue of an outstanding detergency action coupled with an excellent ability to prevent soil redeposition on the materials treated.

It is another object of this invention to provide an improved process of dry cleaning in chlorinated dry cleaning solvents.

It is a further object of this invention to provide an improved process of dry cleaning wherein chlorinated dry cleaning solvents are employed in conjunction with minor amounts of water.

According to the present invention the new compositions thereof, hereinafter termed dry cleaning compositions, to be incorporated in the chlorinated dry cleaning solvents contain as the essential components thereof a cationic surfactant derived from fatty .amines and an alkylene oxide and a mixture of a nonionic and an anionic surfactant;

Compositions as above described give particularly outstanding results in chlorinated dry cleaning solvents. In addition, they give excellent results where a small amount of water has been incorporated into the dry cleaning solvent for the purposes described above. Among the chlorinated dr cleaning solvents one may use and which are nor-many employed in dry cleaning operations are the following:

Trichloroethylene Tetrachlor'oethylene Carueu'tetrsemeriaesua the like 2,980,624 Patented Apr. 18, 1961- ICQ The cationic agents which are contemplated in this invention are derived, as described above, from fatty amines reacted with alkylene oxides or their equivalent. The fatty amines which are employed herein are those amines which contain at least 75% unsaturated linkages therein, of which at least 35% are of the double unsatura-- tion type. Since such amines are usually obtained from natural fatty oils, they are usually employed as mixtures which mixtures correspond to the composition of the naturally occurringoils. Thus, an outstanding and preferred amine identifiable as a soybean amine is derived from the soybean oil fatty acids'by ammonolysis and reduction to give a mixture of amines of the following approximate composition:

Percent Octadecadienyl amine 45 Octadecenyl amine 35 Octadecyl amine l Hexadecyl amine saturates of which 45% are of the diethenoid type.

. in U,

It will be noted that this mixture contains 80% un- It is of course, possible to employ in the preparation of the compositions of this invention synthetically prepared mixtures from the various amines within the scope of this invention and it is further possible to employ the pure unsaturated amines provided they come within the scope of the above limitations. In addition to soybean amine, numerous other fatty oils are suitable as precursors for the amines operable in this invention. Such fatty oils include cottonseed oil, corn oil, sesame oil, sunflower seed oil and-the like. The approximate acid constituents of these oils are given below:

Saturated acids and neutral mate'als Remainder Linoleic 'acid 57 Oleic acid p 33 Saturated acids and neutral materials Remainder Amines derived from these oils in the manner of that described above for soybean amine will contain at least of the amine constituent as unsaturates of which amount at least 35% will represent doubly unsaturated compounds. in addition to the above mentioned fatty oils it is also possible to employ other naturally occurringmaterials which, upon suitable treatment by hydrolysis, ammonolysis and reduction, yield an amine or mixtures of amines coming within the scope of the limitations described above as to the unsaturate content thereof. The cationic agent suitable for use in the compositions of this invention are prepared from the above described amines or mixtures of amines by well known reactions with alkylene oxidesor their equivalents. The polyoxyalkylated products resulting vfrom such process'es which are suitable for use in this invention are those products which contain from about 14 to about 53% alkylene oxide (1 to 7 moles of alkylene oxide per mole of amine) or its equivalent. Methods for the preparation of such condensation products are described H v atents 1,970,578 and 2,213,477. The nonionic surfactants which are contemplated for use in the prescut invention, as a second essential ingredient thereof, are those characterized as alkyl aryl polyoxyalkylcne glycols. These glycol ethers may be derived in the known manner from alkylated aromatic hydroxy compounds of the benzene and naphthalene series such as p-n-butylphenol, amylcresol, diisobutylphenol, 'diamylphenol, isohexylphenol, oleylphenol, isododecylphenol, tetradecylphenol, isooctylresorcinol, nonylphenol, dinonylphenol, isooctyiphenol, isooctyl-p-naphthol, ,isohoxylxylenol, n-octadecylphenol, and the like. In general,

' these alkylated aromatic hydroxy compounds should contain at least one alkyl radical of at least 4 carbon atoms as a ring substituent. It will be understood that such compounds may contain up to 3 alkyl substituents which may be straight or branched, which substituents' may contain a total of 20 or more carbon atoms: j

These alkylarylhydroxy compounds are polyoxyalkylenated by reaction under proper conditions, preferably in the presence of an alkaline catalyst such as potassium hydroxide or sodium hydroxide, and .heat and pressure, with from 3 to 7 molesof an alkylene oxide such as ethylene oxide, propylene'oxide, or the like, or mixtures thereof. j

The anionic surfactants to be employed as the third essential ingredient of the compositions of this invention comprise the anionic salts derived from the abovementioned nonionic. glycols. These anionic salts are readily prepared fromsaid nonionic compounds by subjecting the glycol ether to esterification with a strong acid such as chlorosulfonic, sulfamic, sulfuric, or phosphoric or with an inorganic acid anhydride such as sulfur trioxide or phosphorus pentoxide or with acid halides such as sulfury l chloride, phosphorus oxychloride or phosphorus pentachloride and the like. When a properly substituted acid mixture is employed in the esterification such as aminosulfonic acids, sulfamic acid, ammonium bisulfate, and the like, a water-soluble or dispersible salt is directlyproduced without the necessity of subsequent neutralization with a basic substance. In such cases, subsequent treatment with basic materials is only for the purpose of neutralizing excess acid, and the like. Excellent results are also obtained when coinplexes of some of the above acids and anhydrides are employed. For example, a combination of sulfur trioxide or chlorosulfonic acid with an ether such as diox ane, thioxane or ,8,5'-dichlorodiethylether, or with a tertiary nitrogen base such vas pyridine or triethylamine may be used. The resulting esters may be neutralized with a basic material such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate, ammonium hydroxide, ammonia, calcium oxide .and bydroxide, magnesium oxide and hydroxide, strontium hydroxide, ethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, triethylamine, diethylamine, butylamine, propylamine, cyclohexyloamine, morpholine, pyridine, octanolamine, octylamine, and the like.

The greatest values to be derived from this invention lie not only in the superior detergent action of the dry cleaning compositions thereof but further, in the outstanding characteristics of soil redeposition prevention and whiteness retention which are evident in chlorinated dry cleaning solvents. In order to achieve the excellent and superior effects to be derived from the use of the compositions of this invention, the proportions of the various ingredients thereof must be employed withiril certain critical limits. The cationic surfactant which, as described above, is of the polyoxyalkylated-unsaturatedamine type, should comprise at least 15% one volume basisv of the total surfactants present, and no more than about 50%. The above described anionic agents should be employed within the range of 8.5 to 50% on a vol-f on a volume basis of from 35 to 76.5% based on the 1 50 /2 in. steel balls 50 ml. of solvent 1 3% in. diameter circular swatch of acetate iersey or Botany wool flanneL soiled or unsoiledyas indicated below: I 1

The 8 jars contained thefollowingz TABLE I Jar N o Launder-Ometer 'Iest Components Test Acetate jersey soiled swatch-.. detergency.

Wool flannel soiled swatch. Do. Acetate jersey soiled swatch, detergent wet Do.

stock. l Wool-flannel soiled swatch, detergent wet stocln Do.- I K Unsoiled acetate jersey swntch,-5 mg. synthetredeposltion.

10 dry soil. Unsoiled acetate wool flannel swatch, 5 mg. Do.

synthetic dry soil. I 7 Unsoiled acetate jersey swatch, 5 mg. synthet- Do.

' ic dry soil, detergent wet stock.- 8 Unsoiled wool flannelswatch, 5 mg. synthetic Do: dry soil, detergent wet stock. v

The synthetic dry soil used in the above tests has the following composition:

TABLE 11 Synthetic soil composition Ingredients mixed as follows:

The above was mixed; in a ball mill until heterogeneous.

The oils listed below were melted and blended by hand into the powdered mixture.- They were:

Components Percent Grams stearic acid 1. t3 16. 0 id 1. 6 16. 0 0161 c 3. 2 32. 0 3 18-3 lanolin anhydride (Merck) 1. I

m-octadecane (Conn. hard rubber) 1. 1 11. 0 1-octadeccne (Humphrey Wilkinson)- 1. 1 11.. 0

1500 ml. H O were added. The mixture was ball milled 3 for 16 hours and dried. The dried soil then was pul-.

ume basis based on the total surfactants present. The

nonionic compounds should be. employed in amounts verized in a hammer mill to approximately 200 mesh.

The cloth used for detergency testswas -soilcd by padding in the Butterworth three-roll padder, giving 3 passes through a 5% suspension'of the synthetic dry soil in Stoddard Solvent and air drying the cloth. All cloth was stored in a constant humidity chamber prior to use at a relative humidity of 50 to, 63%.

The test conditions were as follows:

In the. following examples which will serve to exem In the foregoing table, column'l indicates the detergent.

plify the compositions and processes of thisinventiomit tested, column 2 the fabric, which is prepared for the will be understood that such exemplification'is not deemed detergency tests as described above. Column 3 lists the to be limitative of the invention herein covered. In the solvents employed, column 4, the detergency efliciency said examples, parts indicates parts on a volume basis 5 where one is employed, based on reflectance readings.

unless otherwise indicated. The standard is taken as a magnesium oxide block: 100. The unsoiled rayon and wool have varying degrees of EXAMPLE 1 whiteness andtherefore the significant values are the Atmlxmrevofi differences appearing in columns 5 and 7. Thus the larger the value in column 5 the better is the cleaning 5 Pam M a blend com-pnsmg the following mgredlems' action of the composition. The smaller the figure in 5 parts alkyl Y i W i with column-7fthe better is the composition for preventing 3 ggi g salt of the soil redeposition. The figures in column 6(a) are the 1 part Of a ifatlomc Prepared 'Q ne 15 column 6(b) the values for the same swatches put through s y ean amllw contammg 33% ethylen? oxlde a cleaningcycle as indicated in Table I for jars 5-8.

' d In the following Examples 3 through 14, the compo 15 Prepare nents which are employed are the same as the three components of Examples 1 and 2 except that the proportions Th com osition of the amine recursor com ounds' e p I P I 7 used are varied in accordance with the values given in ll was to ows Percent the tabulation appearing below. In each instance the octadecadienyi amine 45 d t rgency efficiency and whiteness retention characterisoctadecenyl amine g t cs are comparable to those obtained with the composi octadecyl amine 10 trons of Examples 1 and 2. Hexadecyl amine 10 TABLE IV In Table III which follows there is set forth the efficiency of this formulation and a comparison with other com- B A O D rnercial formulations and with a control solvent contain Example Cationic Anionic Nomomc Ratio mg no detergent. Agenty Agent, A ent; 0113 EXAMPLE 2 e Percent Percent Percent A mixture of 1o 45 9:2 2 parts of a blend comprising the following ingredients: g g 5 parts alkyl aryl polyoxyethylene glycol} with 48 13 39 3:1 3 parts of ammonium salt of the sulfur-ic acid ester fig g thereof 40.5 I 8.5 51 6:1 2 parts of a cationic surfactant prepared from refined fig Q soybean amine containing 33% ethylene oxide I 15 51 34 1.5 1 2 parts Stoddard Solvent g2 g3 g8 23% is P P l Soybean amine-ethylene oxide condensate of Example 1.

The efiiciency of this formulation is given in Table I Ammonium salt of the sulfuric ester of the nonionic agent or Ex. 1. HI below: V Dinonyl phenol-ethylene oxide condensate of Ex. 1.

In the following Examples 15 through 26, the anionic d 1fd"' h 1th! Con pro net of amonyl p i w and nomomc agents are the same as those described above moles of ethylene oxide.

a T TABLE III Reflectance Readings 1 2 3 Detergency whiteness Retention (a) (6) (b) Detergent Fabric Solvent Boiled Cleaned Before After Cleaning Cleaning rayon 33.0 56.1 24.1 77:5 74.2 2.8 wool 25.0 37.0 12.0 63.9 59.0 4.9 rayon. 34. 7 72. 5 37. 8 78. 0 76. l 1. 9 wo0l.... 25.2 '51.0 25.8 '6520 62.2 2.8 rayon... 38.0 50.0 12.0 78.8 69.9 8.9 wool. 26. 3 37. 0 l0. 7 64;" 0 53. 2 10. 8 rayon. 36. 0 68. 9 32. 9 79. 0 74. 0 5.0 WOOL... 25.6 49.9 24.3 63.9 60.5 3.4 rayon... 30.6 '34.0 3.4 78.8 58.3 20.5 w'ool- 24. 0 1 23-3 62.0 47. 1 14. 9 rayon 36. 0 45. 9 9. 9 78. 0 58. 0 20. 0 23.9 31.1 7.4 63.6 55.5 18.1 34.3 3 64.0 29.7 77.4 72.5 4.9 Do 24.7 37.0 12.3 64.5 57.5 17.0 Commercial AgentB rayon... 36.2 65.6 29.4 77;? 67.8 9.9 Do. wool---. PO 24.4 48.4 24.9 64.4 67.9 6.5

Acetateiersey. j Woolflannel; Perchlorothylene.

. t The "cleaned" wool was not cleaned in tin: test. 'lhesc agents useflfl in PGE only. a 1

values-obtained for unsoiled -untreated fabrics, those of 7 but the cationic agents AA and AB are, respectively, soybean amine condensation products containing 14% ethylene oxide and 53% ethylenefoxide. 'Again, the results obtained in the. detergency tests and whiteness retention tests show these compositions to be comparable in these characteristics to the compositions described above.

AA is a soybean amine-ethylene oxide condensate containing 14% ethylene oxide.

1 AB is a soybean amine-ethylene oxide condensate containing 53% ethylene oxide.

8 Ammonium salt of the sulfuric ester of the nonionic agent of Ex. 1.

i Dinonly phenol-ethylene oxide condensate of Ex. 1.

In the following Examples 27 through 38, the anionic (b) corn oil amine containing 33% ethylene oxide, and (c) sesame oil amine containing 53% ethylenei'oxide. The results in so far as detergency value and whiteness retention characteristics are concerned are equivalent to those obtained above.

TABLE VI I [I III 11 Example Cationic Agent Anionic Nonionic Bat Agent 4 Agent 1 111:11 A0 AD= All g 1 A0 is cottonseed amine containing 14% ethylene oxide.

2 AD is corn oil amine containing 33% ethylene oxide. v 3 AB is sesame oil amine containing 53% ethylene oxide.

Ammonium salt of the sulfuric ester of the nonionic agent 0! Ex. 1.

E Dinonyl phenol-ethylene oxide condensate of Ex. 1. I v Norm-The values given in the table above refer to parts.

' In the following Examples 39Ithrough 93 set forth in Table VII, various compositions within the ambit of and nonlonic surfactants employed are snmlar to those this invention are shown. These compositions exh bit used in the previous examples. The cationic agents are excellent detergent andwh teness retention abihtles. The (a) cottonseed amme containing 14% ethylene oxide; figures g1ven indicate parts.

TABLE VII I v n m Ratio of Example Anionic Agent N onionie Agent Nonionio Cationic to- 2 Agent Anionic R s T U V W x Y 11 31 5:3 11 31 50 5:3 11 50 5:3 11 31 50 5:3 11 50 6:3 50 19 .32 2:1 50 32 2:1 50 v 18 32 2:1 50 18 :12 2:1 50 1s 32 2:1 15 8.5 76.5 9:1 15 8.5 76.5 9:1 15 8.5 76.5 9:1 15 8.5 76.5 9:1 15 8.5 76.5 9:1 29 1o 1:1 20 1o 70 7 1:1 20 10 10 1:1 20 10 10 1:1 20 10 10 -1:1 49 1a 39 3:1 48 13 v 39 3:1 48 13. 38 9:1 48 13 39 3:1 48 13 39 3:1 30 35 35 1 1:1 30 35 35 1:1 :10 35 35 1:1 30 35 35 1:1 30 35 35 1:1 15 51 .34 1:11 15 51 34 1:1.5 1s 51 e4 1:1.5 1:: s1 34 1: a 15 51 34 1: 5 1.1 8.5 76.5 9:1 15 8.5 76.5 9:1 is 8.5 76.5 9:1 15 8.5 76.5 9:1 15 8.5 76.5 9:1 46 9 45 5:1 46 9 45 5:1 46 9 45 5:1 .45 9. 45 J11 46 9 45 5:1 30 35 35 1:1 30 35 35 1:1 30 35 '35 1:1 30 '35 35 1:1

9 TABLE VII-.Continued a.-The cationic agent of Example 1 is employed. 15.-The cationic agent of Example 15 is employed. c.The cationic agent of Example 18 is employed. d.The cationic agent of Example 27 is employed. e.The cationic agent of Example 31 is employed. j.Ihe cationic agent of Example 35 is emplo yed. 1 R is the sodium salt of the sulfuric acid ester oi the nonionic in each example where R is used.

2 S is the ammonium salt of the sulfuric acid ester of the nonionic in each example where S is used 3 T is the sodium salt of the sulfuric acid ester of the nonionic of each example where T is useq'U is a nonionic from nonyl phenol with 7 moles ethylene oxide.

I V is a nonionic from nonyl phenol with 5 moles ethylene oxide.

W is a nonionic from nonyl phenol with 3 moles ethylene oxide.

1 X is a nonionic from tetradecyl phenol with 7 moles ethylene oxide.

Y is a nonionic from lsoctyl phenol with 7 moles ethylene oxide.

This invention has been disclosed with respect to certain preferred embodiments. Various modifications and variations of these embodiments will become apparent to those skilled in the art, and it is to be understood that such modifications and variations are to be included within the spirit and purview of this application and the scope of the appended claims.

I claim:

1. A composition adapted for use in the dry cleaning of textile and fibrous materials in chlorinated hydrocarbon dry cleaning solvent consisting essentially of a surface active agent mixture for each 100 parts of which there are present at least parts of a polyoxyalkylated fatty amine surface active agent containing from about 14% to about 53% alkylene oxide, the said amine containing at least 35% octadecadienyl amine and the balance of said mixture a mixture of an anionic and an alkyl aryl polyoxyalkylene glycol ether nonionic surface active agent, the components of said mixture being present in the ratio of from about 1:9 to 1.511, the anionic surface active agent being selected from the group consisting of the sulfate and phosphate esters of alkyl aryl polyoxyalkylene glycols.

2. A composition as set forth in claim 1 wherein the fatty amine surface active agent is a soybean amine containing 14% ethylene oxide.

3. A composition as set forth in claim 1 wherein the fatty amine surface active agent is a soybean amine containing 33% ethylene oxide.

4. A composition as set forth in claim 1 wherein the fatty amine surface active agent is a soybean amine containing 53% ethylene oxide.

5. A composition as set forth in claim 3 wherein the ratio of anionic to nonionic surface active agent is about 2:1.

6. A composition as set forth in claim 3 wherein the ratio of anionic to nonionic surface active agent is about 1:1.5.

7. A composition adapted for use in the dry cleaning of textile and fibrous materials in chlorinated hydrocarbon dry cleaning solvent consisting essentially of a surface active agent mixture for each 100 parts of which there are present at least 15 parts of a polyoxyalkylated fatty amine cationic surface active'agent containing at least 35% octadecadienyl amine and containing from 1 about 14% to about 53% alkylene oxide, from about 35 parts to about 76.5 parts of an alkyl aryl polyoxyalkylated glycol nonionic surface active agent and from about 8.5 parts to about 50 parts of a salt of an ester selected from the group consisting of sulfate and phosphate esters of said nonionic surface active agent.

8. A composition as defined in claim 7 wherein the cationic surface active agent is a soybean amine containing about 33% ethylene oxide, the nonionic surface active agent is a glycol derived from dinonylphenyl condensed with about 7 moles of ethylene oxide and the anionic surface active agent is the ammonium salt of the sulfuric acid ester of said nonionic surface active agent.

9. A composition as defined in claim 7 wherein the cationic surface active agent is a soybean amine containing about 14% ethylene oxide.

10. A composition as defined in claim 7 wherein the cationic surface active agent is a soybean amine containing about 53% ethylene oxide.

11. A composition as defined in claim 7 wherein the cationic surface active agent is a cottonseed amine, the nonionic surface active agent is a glycol derived from nonylphenol condensed with about 5 moles of ethylene oxide and the anionic surface active agent is the ammonium salt of the sulfuric acid ester of said nonionic surface active agent.

12. A composition as defined in claim 7 wherein the cationic surface active agent is a corn oil amine, the nonionic surface active agent is a glycol derived from isooctyl phenol condensed with about 7 moles of ethylene oxide and the anionic surface active agent is the ammonium salt of the sulfuric acid ester of said nonionic surface active agent.

13. A composition as defined in claim 7 wherein the cationic surface active agent is a sesame'oil amine, the nonionic surface active agent is a glycol derived from nonylphenol condensed with about 3 moles of ethylene oxide and the anionic surface active agent is the ammonium salt of the sulfuric acid ester of said nonionic surface active agent.

14. A composition as defined in claim 8 wherein the cationic, anionic and nonionic surface active agents are in the ratio of about 3:2:1.

15. A composition as defined in claim 8 wherein the cationic, anionic and nonionic surface active agents are in the ratio of about 2:0.75:1.25.

References Cited in the file of this patent UNITED STATES PATENTS (Other references on following page) .11 UNITED STATES PATENTS 2,697,075

Borus et a1. May 30, 1950 2,721,847' Larchar Aug. 8, 1950 2,733,212 Isbell Nov. 25, 1952 2,778,814 Zussman et a1. Feb. 16,1954 5 12 Echols Dec. 14, 1954 Gebhart et a1. Oct. 25, 1955 Epstein et a1. Jan. 31, 1956 Behrens et a1. Ian. 22 1957 FOREIGN PATENTS Great Britain May 4, 1955 

1. A COMPOSITION ADAPTED FOR USE IN THE DRY CLEANING OF TEXTILE AND FIBROUS MATERIALS IN CHLORINATED HYDROCARBON DRY CLEANING SOLVENT CONSISTING ESSENTIALLY OF A SURFACE ACTIVE AGENT MIXTURE FOR EACH 100 PARTS OF WHICH THERE ARE PRESENT AT LEAST 15 PARTS OF POLYOXYALKYLATED FATTY AMINE SURFACE ACTIVE AGENT CONTAINING FROM ABOUT 14% TO ABOUT 53% ALKYLENE OXIDE, THE SAID AMINE CONTAINING AT LEAST 35% OCTADECADIENYL AMINE AND THE BAL ANCE OF SAID MIXTURE A MIXTURE OF AN ANIONIC AND AN ALKYL ARYL POLYOXYALKYLENE GLYCOL ETHER NONIONIC SURFACE ACTIVE AGENT, THE COMPONENTS OF SAID MIXTURE BEING PRESENT IN THE RADIO OF FROM ABOUT 1:9 TO 1.5:1, THE ANIONIC SURFACE ACTIVE AGENT BEING SELECTED FROM THE GROUP CONSISTING OF THE SULFACT AND PHOSPHATE ESTERS OF ALKYL ARYL POLYOXYALKYLENE GLYCOLS. 